JPS6383003A - Mildew-proofing agent - Google Patents

Abstract

PURPOSE:To obtain a mildew-proofing agent having controlled rate of dissipation of the active component and prolonged activity, by using a specific fumaric acid diester or maleic acid diester and a specific methylated cyclodextrin and its derivative as active components. CONSTITUTION:The objective mildew-proofing agent contains (A) 0.1-10.0wt% diethyl ester compound of formula I (R1 and R2 are 1-10C alkyl) (e.g. dimethyl maleate) and (B) 1/2-20pts.wt. (based on 1pt.wt. of the diethyl ester compound) of a cyclodextrin or its derivative, especially a methylated cyclodextrin of formula II (A is methyl or H; n is 6-9; at least one of the 3n A groups is methyl), above all a methylated cyclodextrin having a weight-average ether- substitution degree of 8.0-11.0 and containing >=50wt% methylated beta- cyclodextrin having an ether substitution degree of 8-11. The agent can be applied in various forms.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a mold inhibitor, and more particularly to a mold inhibitor containing a specific diester compound and a specific methylated cyclodextrino, which has good persistence and excellent effects. Concerning anti-mold agents.

[Conventional technology]

In our daily lives, we often suffer from damage due to neglect of mold and insect control, and interest in these matters is increasing.

In recent years, due to changes in the structure of houses, indoor airtightness has increased.
The areas where mold damage occurs are not only in areas where moisture is involved, such as kitchens and bathrooms, but also in areas such as geta boxes.

BACKGROUND ART Conventionally, in order to prevent mold from forming, a liquid agent containing a mold preventive agent such as thiabendazole is applied to building materials and wood for houses.

In addition, insect repellents for clothing such as no9razochlorobenzene, naphthalene, and camphor are used for textile and leather products such as clothing, bags, and shoes.

[Problem that the invention seeks to solve]

Although the above-mentioned thiapendazole has high anti-mildew properties, it hardly evaporates at room temperature, so it must be applied evenly to all parts to be anti-mildew, but this poses many problems in terms of toxicity. For this reason, the use of α-bromocinnamic aldehyde or 9-chloromethaxylenol may be considered, but these also have low volatility at room temperature and have the same problems as above. On the other hand, the conventionally used insect repellents, such as 9-razochlorbenzene, naphthalene, and camphor, are volatile and have some, if not sufficient, antifungal properties; The compound has a strong odor and may be unpleasant for some people.

For this reason, JP-A No. 61-60602 proposes a mold-proofing agent for spaces using maleic acid zoester. These compounds have volatile properties at a constant temperature and are highly effective in preventing mold. In addition, these diester compounds are impregnated into a carrier such as paper and treated to prevent mildew, but in order to maintain the effect of the drug for a long time, the diester compound-treated carrier is treated with a diester compound. Can't pass through? Can you cover it with a sheet of lysologylene or the like and leave part of it open during use, or cover it with a sheet of y% IJ ethylene through which the diester compound permeates little by little to control volatilization? Efforts have been made to do this by adjusting the thickness of the polyethylene sheet. However, it is strictly difficult to control volatilization with these sheets, and depending on how they are used, the sheets may break or become damaged, leading to problems such as the drug evaporating from the damaged parts of the sheet in a short period of time. have.

For this reason, there has been a desire for a method that can easily and reliably control the volatilization of antifungal agents using specific fumaric acid zoesters and maleic acid zoesters.

[Failure to solve the problem]

As a result of intensive research to develop a mold inhibitor that satisfies the above requirements, the present inventors have developed a mold inhibitor by treating a specific zoester compound, which is volatile and has an excellent mold prevention effect, with cyclodextrin and its derivatives. The present invention was completed based on the discovery that the volatilization of the drug can be controlled, the persistence of the drug can be improved, and the range of usable dosage forms can be expanded.

That is, the present invention provides the following components (8) and The present invention provides a mold inhibitor characterized by containing a compound represented by (B) (A) in an amount of 3A to 20 times the weight of cyclodextrin or a derivative thereof.

Conventionally, cyclodextrin has been known to form clathrate compounds with various substances, and also includes substances having various mold-preventing effects.

Using this principle of inclusion, for example, JP-A-52-15
No. 809 discloses a method of including iodine with β-cyclodextrin to increase stability and controlling volatilization, and JP-A-55-87701 discloses a method of including iodine with β-cyclodextrin. A method for providing sustainability is disclosed.

The zoester compound used in the present invention exhibits lipophilic properties that hardly dissolve in water.

For this reason, conventional methods for utilizing zoester compounds have been to impregnate paper, chlorine, etc., or to absorb and retain them in mineral powders such as talc or kaolin, and to place them at the location of use. However, the volatilization of the zoester compound cannot be controlled by the method of absorbing it into these holding agents, and therefore, as described above, the method of covering it with various films has been used to control it. However, according to the method using the clathrate compound of the present invention,
Volatile cone) can be made without using any glue film, and it can also be used as a powder, which can be used not only in spaces but also by kneading into food and adhesives, expanding the range of applications of zoester compounds. becomes possible.

(B) Among the components, general formula (6) (wherein A represents a methyl group or a hydrogen atom, and n represents a number from 6 to 9. However, at least one of the 3n A's is a methyl group) The methylated cyclodextrin represented by the following formula is particularly preferable since the methylated cyclodextrin in which component (A) is included dissolves well in water.

That is, a methylated cyclodextrin containing component (A) dissolves at least 10% by weight in water at room temperature, so it can be added to most foods and water-soluble adhesives.

n of the methylated cyclodextrin of general formula (II)
is 6, methylated α-cyclodextrin, n is 7
The one in which n is 8 is called methylated β-cyclodextrin, the one in which n is 8 is called methylated γ-cyclodextrin, and the one in which n is 9 is called methylated δ-cyclodextrin, and all of these exhibit clathrate-forming properties. Among these, methylated β-cyclodextrin with a degree of ether substitution of 8 to 11 is 50% by weight upwind, and the weight average degree of ether substitution is 8.
Those containing methylated β-cyclodextrin having a molecular weight of 0 to 11.0 are preferred. Here, the degree of ether substitution refers to the number of methyl groups introduced per cyclodextrin molecule, and in a mixture containing two or more methylated cyclodextrins with different degrees of ether substitution, the degree of ether substitution and the weight percent of each component From this, the weight average degree of ether substitution is calculated.

Methylated cyclodextrin (B) is produced by methylating cyclodextrin according to a conventional method. When cyclodextrin is methylated using a known methylating agent such as dimethyl sulfate, a mixture is obtained in which the hydroxyl groups of glucose residues are methylated in the order of 6-, 2-, and 3-positions. In the present invention, it is sufficient that at least one of the 3n A's in general formula (6) is a methyl group.

In addition, examples of the diester compound of component (8), which is an active ingredient of the mold inhibitor of the present invention, include zomethyl maleate,
aethyl maleate, zopropyl maleate, sibutyl maleate, zopentyl maleate, zohexyl maleate, zohezotyl maleate, zooctyl maleate, zononyl maleate, so7”/l maleate, zomethyl fumarate, zoethyl fumarate, 7mal Acid Zozorogil,
Examples include sibutyl fumarate, zopentyl fumarate, zohexyl fumarate, zohezotyl fumarate, zooctyl fumarate, zononyl fumarate, zodecyl fumarate, and the like.

The amount of ingredients added to the mold inhibitor of the present invention is 0.01 to 1
It is 0.0% by weight (hereinafter simply indicated as "chi"). Also,
Component (B) is used in a weight ratio of % to 20 times, preferably 1 to 10 times, relative to component (A).

Even if component (B) is added in an amount less than % by weight of component (A), there is almost no effect on increasing stability, and even if it is used in an amount exceeding 20 times, there is no further increase in stability. No enhancement is seen.

The mold inhibitor of the present invention is produced by blending the above two components, but in order to sufficiently clathrate the diester compound into the cyclodextrin etc., it is preferable to treat the zoester compound with cyclodextrin etc. in advance. . In addition, methods for treating the zoester compound with cyclodextrin etc. include a saturated aqueous solution method in which the zoester compound is added to a saturated aqueous solution of cyclodextrin etc., and a kneading method in which the cyclodextrin etc. and the zoester compound are kneaded together with a relatively small amount of water using a kneader etc. Law etc. will be adopted.

In addition to the above-mentioned essential components, the fungicide of the present invention may contain various additives commonly used in such cases, and may also contain drugs having various insect repellent effects.

Examples of these optional components include antioxidants such as BHT and BHA; perfumes, surfactants, camphor, camphor, and norazochlorbenzene.

〔Effect of the invention〕

According to the present invention, the zoester compound (Siflovkis)
Inclusion with IJ or its derivatives controls the volatilization of the zoester compound, thereby greatly reducing the number of formulation steps.

Furthermore, although the zoester compound is insoluble in water, an aqueous solution can be made by including it with cyclodextrin, and the range of applicable dosage forms can be expanded.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 10% zomethyl maleate, 86% β-cyclodextrin and 4% water were mixed using a strainer (mixing method) to obtain a β-cyclodextrin clathrate of zomethyl maleate. 20% of this inclusion, 30% lactose and 5
Compressed into tablets with 0% talc and 2% zomethyl maleate.
A tablet-shaped anti-mold agent was obtained.

Example 2 10% zomethyl 7malate, 4% water and 86% β-
The cyclodextrin was thoroughly mixed and kneaded using a sieve machine to obtain a clathrate of β-cyclodextrin and zomethyl fumarate. 30% of this clathrate compound, 40% of lactose, and 30% of potato dendenate are kneaded with a 5% ethanol solution of ethyl cellulose, granulated with an 8-mesh wire mesh, and then dried at room temperature to form granules containing 3 parts of zoethyl fumarate. A mold inhibitor was obtained.

Example 3 10 ml of zomethyl maleate, 4% of water and 86% of methylated β-7 clodextrin (weight average degree of ether substitution 9.0) were mixed and kneaded using a sieve machine), maleic acid A methylated β-cyclodextrin inclusion product of zomethyl was obtained. 20% of this clathrate, 30% lactose and 5%
Compressed into tablets with 0% Merck and 2% zomethyl maleate.
A tablet-shaped anti-mold agent containing the following was obtained.

Example 4 10 or more zoethyl fumarate, 4% water and 86% methylated β-cyclodextrin (weight average degree of ether substitution 8.0) were mixed using a sieve machine (mixing method), zoethyl fumarate A methylated β-cyclodextrin inclusion product was obtained. 30% of this clathrate compound, 40% of lactose, and 30% of potato starch are kneaded with a 5% ethanol solution of ethylcellulose, granulated using an 8-mesh wire mesh, and dried at room temperature to form granules containing 3% of zoethyl fumarate. A mold inhibitor was obtained.

Example 5 20% zoethyl maleate, 5% water and 75% methylated β-cyclodextrin (weight average degree of ether substitution 9.4) were kneaded using a sieve machine (mixing method), maleic acid A zoetel inclusion product was obtained. 10% of this clathrate was dissolved in 90% water to obtain a bactericidal aqueous solution containing two doses of zoethyl maleate.

Example 6 The mold inhibitor produced in Examples 1 to 4 was 64X38X2
A predetermined amount was placed in a 2 m plastic case with a lid, and the residual rate (%) of the active ingredient was measured over time. As a comparative product, we manufactured a product in which cyclodextrin was replaced with talc in the tablets and potato denzone in the granules.
Control examples 1 to 4 were used.

The results are shown in Table-1. The product of the present invention has controlled volatilization and increased durability compared to comparative products.

Margin table below -1 Example 7 The aqueous disinfectant solution produced in Example 5 was mixed with commercially available miso, soy sauce, and sauce so that the concentration of zomethyl maleate was 0.1%, and the mixture was placed in a container without a lid. The samples were stored at room temperature, and the appearance and odor were observed after 2 and 4 weeks. As control products, commercially available miso, soy sauce, and sauce were used as they were.

The results are shown in Table-2. No mold growth was observed in the miso, soy sauce, and sauce to which the products of the present invention were added.

Table 2 Example 8 The disinfectant aqueous solution prepared in Example 5 was commercially available, d IJ
2% in a water-soluble adhesive whose main component is vinyl alcohol.
Added. Apply this material to the wood surface and heat at 40℃ for 8
It was left in a constant temperature room with 0% head and the surface was observed. As a control product, a commercially available adhesive was used as is.

The results are shown in Table-3. No black stains due to mold were observed in the adhesive containing the product of the present invention.

Table-3

Claims (1)

[Claims] 1. General formula (I) of the following components (A) and (B) (A) 0.1 to 10.0% by weight ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) ( In the formula, R_1 and R_2 each represent an alkyl group having 1 to 10 carbon atoms. Anti-mold agent. 2. Cyclodextrin derivatives have the general formula (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) (In the formula, A represents a methyl group or a hydrogen atom, and n is 6 to 9.
Indicates the number of The anti-mold agent according to claim 1, which is a methylated cyclodextrin represented by: 3. Methylated cyclodextrin has a degree of ether substitution of 8
50% by weight of ~11 methylated β-cyclodextrin
or more, and the weight average degree of ether substitution is 8.0 to 11.
2. The mold inhibitor according to claim 2, which has an antifungal agent of 0.